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- In the biosynthesis of heme, ring cyclization, isomerization, and decarboxylation reactions take place. Identify the potential intermediates and show the electron flow in the following diagram. HO,C R1 HO2C- -R2 NH HN- но- NH HN- HO2C R R2 unstable intermediate Uro'gen II HO2C Me Me NH HN- -CO2H HN NH Me Me HO2C CO2H Coproporphyrinogen IIDiscuss the relationship between redox potentials E0’ and the organization of the components of the electron transport chain. Be specific, i.e., use data/actual values to back up your discussion. a) What are the values of E0’ for all the components of the ETS? b)How are the E0’ related to ∆G values? c) How do the values of E0’ vary among the participants in the ETS relative to their position in the ETS?2. a) Energetics of the electron transport. In the oxidative phase of oxidative phosphorylation, electrons are passed from NADH and ultimately to molecular oxygen through an electron transport chain comprised of multiple redox centers. Assume that an electron is passed through the chain along the route shown below. Clearly, there are steps missing, but we will skip those to emphasize the energetics of the electron transport. Calculate DE' and DGº' for each electron transfer step and record the values in the table. The reduction potentials for each of the redox centers are given in table 11.1. (F=96.4 kJ/V mol) Route: NADH → (Fe-S)N-5,6 Coenzyme Q → Cytochrome c₁ → Cytochrome a3 ⇒ 0₂ Table 11.1 STANDARD REDUCTION POTENTIALS (E°') FOR SELECTED ELECTRON CARRIERS IN THE ELECTRON TRANSPORT SYSTEM Electron carriers NAD+ + H+ + 2e → NADH Complex I (NADH-ubiquinone oxidoreductase) Fe-S (N-1b) Fe-S (N-3,4) Fe-S (N-5,6) Complex II (succinate dehydrogenase) FAD + 2H+ + 2e → FADH₂ (enzyme bound)…
- Indicate whether each of the following changes represents oxidation or reduction. Write: O = for oxidation ; R= for reduction Example: cyt ci (Fet) → cyt c1 (Fe2+) Answer: R Blank #1: COQH2 → CoQ Blank #2: NAD+ - NADH Blank #3: FMN → FMNH2 Blank # 4: FADH2 FAD Blank #5: Fe(III) SP → Fe(II) SP Blank # 1 Blank # 2a) Assuming that ubiquinone is unavailable inside of the cell, calculate the AG and the Keq if electrons are transferred directly from complex I to complex III of the electron transport chain. In your answer include the net equation for this electron transfer. Constants: R= 8.3J/degree'mol, F= 96.1kJ/volt mol, T=298K ( Half Reaction EM ubiquinone + 2e + 2H' Ubiquinol + H2 NAD + 2e+ 2H'→ NADH + H 0.045 -0.320 1/202 + 2e +2H H,O Cytc (Fe") + +le + 1H"→ Cytc (Fe²) 0.816 0.254 b) In a single sentence explain whether or not this electron transfer is possible. /2B. Calculate the total number of ATP that will be generated from the complete B-oxidation of oncobic acid (CH:(CH,),CH=CH(CH,),COOH; 15:1 cis-A9) in an organism that has all the standard required enzymes for metabolism but which pumps only 2 H" in complex I, 0 H' in complex II, 2 H* in complex III and 4 H' in complex IV. The F,F, ATPase is composed of 3 a/ß subunits and 10 c subunits. Show all of your calculations. HO
- 16. The overall reaction for the glycolysis reaction is C6H₁2O6(aq) + 2NAD+ (aq) + 2ADP³(aq) + 2HPO(aq) + 2H₂O(1) 2CH3COCO₂ (aq) + 2NADH(aq) + 2ATP4 (aq) + 2H3O+ (aq). What is A,G at chemical equilibrium?6. AG of ATP hydrolysis to ADP and phosphate at 25°C is-30.5 kJ/mol. It means: A) ATP is fast hydrolyzed in aqueous solution, either catalytically or non-catalytically B) at equilibrium concentration of ADP and phosphate are much higher than concentration of ATP C) equilibrium constant for ATP hydrolysis is much less than one reaction of ATP hydrolysis is endergonic D) E) without proper enzyme hydrolysis of ATP does not occur If you have 100 ml. of gastric juice,10) The phosphorylation of glucose is an unfavorable reaction, with ΔG°’ = 13.8 kJ/mol. We can couple this to the favorable reaction of ATP hydrolysis to make the overall process favorable. a) Describe how this works. b) If ΔG°’ for ATP hydrolysis = -32.2 kJ/mol, what is the overall ΔG°’ of the reaction?
- 6F. What conformational state is stabilized by y in ATP synthase? Why might achieving this state require energy input from the PMF?When pure reduced cytochrome c is added to carefully prepared mitochondria along with ADP, Pi, antimycin A, and oxygen, the cytochrome c becomes oxidized, and ATP is formed, with a P/O ratio approaching 1.0.(a) Indicate the probable flow of electrons in this system.(b) Why was antimycin A added?(c) What does this experiment tell you about the location of coupling sitesfor oxidative phosphorylation?(d) Write a balanced equation for the overall reaction (including cyt c oxidation and ATP synthesis).(e) Calculate ΔG°′ for the above reaction, using E′0 values from Table 14.1and a ΔG°′ value for ATP hydrolysis of -32.2 kJ/mol.17. Omeprazole is a bioprecursor prodrug that is activated by protonation to give active metabolite that inhibits H¨,K*-ATPase covalently. By using chemical equations show activation of Omeprazole and its reaction to inhibit the H*,K*-ATPase. CH3 H3CO. s=0 H3C HNN Omeprazole OCH3 18. The following compound is an open-chain prodrug of benzodiazepines which undergo N- dealkylation to triazolam. Using chemical equations show transformation of this prodrug to triazolam. H3C H3C CH3 CH3 triazolam open-chain prodrug of triazolam
